Palladium(II) complex with tetrahydrobenzoxosine: synthesis, electronic and molecular structures

I. V. Bakaev; N. F. Romashev; V. I. Komlyagina; P. A. Abramov; A. V. Piskunov; A. L. Gushchin

doi:10.1134/S0022476622120071

Palladium(II) complex with tetrahydrobenzoxosine: synthesis, electronic and molecular structures

Переведенное название: Комплекс палладия(II) с тетрагидробензоксазинобензоксозином: синтез, электронное и молекулярное строение

I. V. Bakaev, N. F. Romashev, V. I. Komlyagina, P. A. Abramov, A. V. Piskunov, A. L. Gushchin

Факультет естественных наук

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

Аннотация

При взаимодействии бензонитрильного комплекса палладия(II) [Pd(PhCN)2Cl2] с глиоксаль-бис(2-гидрокси-3,5-ди-трет-бутилфенил)имином (H2L) происходит внутримолекулярная перегруппировка H2L в соответствующий тетрагидробензоксазинобензоксозин (L') и его координация к Pd(II) с образованием соединения [Pd(L')Cl2]·(CH3)2CO (1·(CH3)2CO). С помощью рентгеноструктурного анализа определена его кристаллическая структура. Атом Pd в структуре находится в плоскоквадратном окружении из двух атомов Cl и двух атомов N лиганда L'. Проведены квантово-химические расчеты в рамках теории функционала плотности и изучено электронное строение 1. Показано, что связи Pd—N и Pd—Cl носят промежуточный характер. В рамках NBO анализа обнаружены орбитали трехцентровых связей N—Pd—Cl. Образование таких трехцентровых связей можно представить как результат донирования электронной плотности с орбиталей неподеленных электронных пар атомов азота на σ*-орбитали связей Pd—Cl.

Переведенное название	Комплекс палладия(II) с тетрагидробензоксазинобензоксозином: синтез, электронное и молекулярное строение
Язык оригинала	английский
Страницы (с-по)	1963-1972
Число страниц	10
Журнал	Journal of Structural Chemistry
Том	63
Номер выпуска	12
DOI	https://doi.org/10.1134/S0022476622120071
Состояние	Опубликовано - 1 дек. 2022

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2.05 ТЕХНОЛОГИЯ МАТЕРИАЛОВ
1.04 ХИМИЧЕСКИЕ НАУКИ

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@article{7125d438d7b24085ac737569189b7036,

title = "Palladium(II) complex with tetrahydrobenzoxosine: synthesis, electronic and molecular structures",

abstract = "Interaction of the palladium(II) benzonitrile complex [Pd(PhCN)2Cl2] with glyoxal-bis(2-hydroxy-3,5-di-tert-butylphenyl)imine (H2L) induces intramolecular rearrangement of H2L into the corresponding tetrahydrobenzoxazinobenzoxosine (L′), and the coordination of the latter to Pd(II) leads to the formation of [Pd(L′)Cl2]·(CH3)2CO (1·(CH3)2CO). The crystal structure of this compound is determined by XRD. The Pd atom in the structure occurs in a square planar environment of two Cl atoms and two N atoms of the L′ ligand. Quantum chemical calculations within the density functional theory are conducted; the electronic structure of 1 is studied. The Pd–N and Pd–Cl bonds are shown to be intermediate type bonds. Orbitals of N–Pd–Cl three-center bonds are discovered using the NBO analysis. The formation of such three-center bonds can be represented as a result of the electron density donation from the orbitals of nitrogen lone pairs to the σ* orbitals of Pd–Cl bonds.",

keywords = "DFT calculations, XRD, coordination compounds, intramolecular rearrangement, palladium, α-diimines",

author = "Bakaev, {I. V.} and Romashev, {N. F.} and Komlyagina, {V. I.} and Abramov, {P. A.} and Piskunov, {A. V.} and Gushchin, {A. L.}",

note = "ACKNOWLEDGMENTS: The authors thank the Ministry of Science and Higher Education of the Russian Federation (project No. 121031700315-2) and the Common Use Center of NIIC SB RAS for the X-ray diffraction experiment, recording IR and 1H NMR spectra, and for providing computing resources of the computing cluster of NIIC SB RAS.",

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Palladium(II) complex with tetrahydrobenzoxosine: synthesis, electronic and molecular structures. / Bakaev, I. V.; Romashev, N. F.; Komlyagina, V. I. и др.

В: Journal of Structural Chemistry, Том 63, № 12, 01.12.2022, стр. 1963-1972.

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

TY - JOUR

T1 - Palladium(II) complex with tetrahydrobenzoxosine: synthesis, electronic and molecular structures

AU - Bakaev, I. V.

AU - Romashev, N. F.

AU - Komlyagina, V. I.

AU - Abramov, P. A.

AU - Piskunov, A. V.

AU - Gushchin, A. L.

N1 - ACKNOWLEDGMENTS: The authors thank the Ministry of Science and Higher Education of the Russian Federation (project No. 121031700315-2) and the Common Use Center of NIIC SB RAS for the X-ray diffraction experiment, recording IR and 1H NMR spectra, and for providing computing resources of the computing cluster of NIIC SB RAS.

PY - 2022/12/1

Y1 - 2022/12/1

N2 - Interaction of the palladium(II) benzonitrile complex [Pd(PhCN)2Cl2] with glyoxal-bis(2-hydroxy-3,5-di-tert-butylphenyl)imine (H2L) induces intramolecular rearrangement of H2L into the corresponding tetrahydrobenzoxazinobenzoxosine (L′), and the coordination of the latter to Pd(II) leads to the formation of [Pd(L′)Cl2]·(CH3)2CO (1·(CH3)2CO). The crystal structure of this compound is determined by XRD. The Pd atom in the structure occurs in a square planar environment of two Cl atoms and two N atoms of the L′ ligand. Quantum chemical calculations within the density functional theory are conducted; the electronic structure of 1 is studied. The Pd–N and Pd–Cl bonds are shown to be intermediate type bonds. Orbitals of N–Pd–Cl three-center bonds are discovered using the NBO analysis. The formation of such three-center bonds can be represented as a result of the electron density donation from the orbitals of nitrogen lone pairs to the σ* orbitals of Pd–Cl bonds.

AB - Interaction of the palladium(II) benzonitrile complex [Pd(PhCN)2Cl2] with glyoxal-bis(2-hydroxy-3,5-di-tert-butylphenyl)imine (H2L) induces intramolecular rearrangement of H2L into the corresponding tetrahydrobenzoxazinobenzoxosine (L′), and the coordination of the latter to Pd(II) leads to the formation of [Pd(L′)Cl2]·(CH3)2CO (1·(CH3)2CO). The crystal structure of this compound is determined by XRD. The Pd atom in the structure occurs in a square planar environment of two Cl atoms and two N atoms of the L′ ligand. Quantum chemical calculations within the density functional theory are conducted; the electronic structure of 1 is studied. The Pd–N and Pd–Cl bonds are shown to be intermediate type bonds. Orbitals of N–Pd–Cl three-center bonds are discovered using the NBO analysis. The formation of such three-center bonds can be represented as a result of the electron density donation from the orbitals of nitrogen lone pairs to the σ* orbitals of Pd–Cl bonds.

KW - DFT calculations

KW - XRD

KW - coordination compounds

KW - intramolecular rearrangement

KW - palladium

KW - α-diimines

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UR - https://www.mendeley.com/catalogue/b3336d96-67be-395d-a62b-21e10b58df59/

U2 - 10.1134/S0022476622120071

DO - 10.1134/S0022476622120071

M3 - Article

VL - 63

SP - 1963

EP - 1972

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 12

ER -